σ-Conjugation and H-Bond-Directed Supramolecular Self-Assembly: Key Features for Efficient Long-Lived Room Temperature Phosphorescent Organic Molecular Crystals

Long-lived room temperature phosphorescence from organic molecular crystals attracts great attention. Persistent luminescence depends on the electronic properties of the molecular components, mainly π-conjugated donor–acceptor (D-A) chromophores, and their molecular packing. Here, a strategy is developed by designing two isomeric molecular phosphors incorporating and combining a bridge for σ-conjugation between the D and A units and a structure-directing unit for H-bond-directed supramolecular self-assembly. Calculations highlight the critical role played by the two degrees of freedom of the σ-conjugated bridge on the chromophore optical properties. The molecular crystals exhibit RTP quantum yields up to 20 % and lifetimes up to 520 ms. The crystal structures of the efficient phosphorescent materials establish the existence of an unprecedented well-organization of the emitters into 2D rectangular columnar-like supramolecular structure stabilized by intermolecular H-bonding.